Entropy-Driven Design of Highly Impact-Stiffening Supramolecular Polymer Networks with Salt-Bridge Hydrogen Bonds.

Impact-stiffening materials that undergo a strain rate-induced soft-to-rigid transition hold great promise as soft armors in the protection of the human body and equipment. However, current impact-stiffening materials, such as polyborosiloxanes and shear-thickening fluids, often exhibit a limited impact-stiffening response. Herein, we propose a design strategy for fabricating highly impact-stiffening supramolecular polymer networks by leveraging high-entropy-penalty physical interactions. We synthesized a fully biobased supramolecular polymer comprising poly(α-thioctic acid) and arginine clusters, whose chain dynamics are governed by highly specific guanidinium-carboxylate salt-bridge hydrogen bonds. The resulting material exhibits an exceptional impact-stiffening response of ∼2100 times, transitioning from a soft dissipating state (21 kPa, 0.1 Hz) to a highly stiffened glassy state (45.3 MPa, 100 Hz) with increasing strain rates. Moreover, the material's high energy-dissipating and hot-melting properties bring excellent damping performance and easy hybridization with other scaffolds. This entropy-driven approach paves the way for the development of next-generation soft, sustainable, and impact-resistant materials.

Hydrogen Bonding Competition Mediated Phase Separation with Abnormal Moisture-Induced Stiffness Boosting.

Moisture usually deteriorates polymers' mechanical performance owing to its plasticizing effect, causing side effects in their practical load-bearing applications. Herein, a simple binary ionogel consisting of an amphiphilic polymer network and a hydrophobic ionic liquid (IL) is developed with remarkable stiffening effect after moisture absorption, demonstrating a complete contrast to water-induced softening effect of most polymer materials. Such a moisture-induced stiffening behavior is induced by phase separation after hydration of this binary ionogel. Specifically, it is revealed that hydrogen (H)-bonding structures play a dominant role in the humidity-responsive behavior of the ionogel, where water will preferentially interact with polymer chains through H-bonding and break the polymer-IL H-bonds, thus leading to phase separation structures with modulus boosting. This work may provide a facile and effective molecular engineering route to construct mechanically adaptive polymers with water-induced dramatic stiffening for diverse applications.

Hydrogels with Differentiated Hydrogen-Bonding Networks for Bioinspired Stress Response.

Stress response, an intricate and autonomously coordinated reaction in living organisms, holds a reversible, multi-path, and multi-state nature. However, existing stimuli-responsive materials often exhibit single-step and monotonous reactions due to the limited integration of structural components. Inspired by the cooperative interplay of extensor and flexor cells within Mimosa's pulvini, we present a hydrogel with differentiated hydrogen-bonding (H-bonding) networks designed to enable the biological stress response. Weak H-bonding domains resemble flexor cells, confined within a hydrophobic network stabilized by strong H-bonding clusters (acting like extensor cells). Under external force, strong H-bonding clusters are disrupted, facilitating water diffusion from the bottom layer and enabling transient expansion pressure gradient along the thickness direction. Subsequently, water diffuses upward, gradually equalizing the pressure, while weak H-bonding domains undergo cooperative elastic deformation. Consequently, the hydrogel autonomously undergoes a sequence of reversible and pluralistic motion responses, similar to Mimosa's touch-triggered stress response. Intriguingly, it exhibits stress-dependent color shifts under polarized light, highlighting its potential for applications in time-sensitive "double-lock" information encryption systems. This work achieves the coordinated stress response inspired by natural tissues using a simple hydrogel, paving the way for substantial advancements in the development of intelligent soft robots.

Entropy-Mediated Polymer-Cluster Interactions Enable Dramatic Thermal Stiffening Hydrogels for Mechanoadaptive Smart Fabrics.

Thermal stiffening materials that are naturally soft but adaptively self-strengthen upon heat are intriguing for load-bearing and self-protection applications at elevated temperatures. However, to simultaneously achieve high modulus change amplitude and high mechanical strength at the stiffened state remains challenging. Herein, entropy-mediated polymer-mineral cluster interactions are exploited to afford thermal stiffening hydrogels with a record-high storage modulus enhancement of 13 000 times covering a super wide regime from 1.3 kPa to 17 MPa. Such a dramatic thermal stiffening effect is ascribed to the transition from liquid-liquid to solid-liquid phase separations, and at the molecular level, driven by enhanced polymer-cluster interactions. The hydrogel is further processed into sheath-core fibers and smart fabrics, which demonstrate self-strengthening and self-powered sensing properties by co-weaving another liquid metal fiber as both the joule heater and triboelectric layer.

Molecular Flexibility of Antibodies Preserved Even in the Dense Phase after Macroscopic Phase Separation.

Antibody therapies are typically based on high-concentration formulations that need to be administered subcutaneously. These conditions induce several challenges, inter alia a viscosity suitable for injection, sufficient solution stability, and preservation of molecular function. To obtain systematic insights into the molecular factors, we study the dynamics on the molecular level under strongly varying solution conditions. In particular, we use solutions of antibodies with poly(ethylene glycol), in which simple cooling from room temperature to freezing temperatures induces a transition from a well-dispersed solution into a phase-separated and macroscopically arrested system. Using quasi-elastic neutron scattering during in situ cooling ramps and in prethermalized measurements, we observe a strong decrease in antibody diffusion, while internal flexibility persists to a significant degree, thus ensuring the movement necessary for the preservation of molecular function. These results are relevant for a more dynamic understanding of antibodies in high-concentration formulations, which affects the formation of transient clusters governing the solution viscosity.

Effect of alpha-lactalbumin and lactoferrin oleic acid complexes on chromatin structural organization.

This work focuses on the study of multimeric alpha-lactalbumin oleic acid and lactoferrin oleic acid complexes. The purpose of the research is to study possible mechanisms involved in their pro-apoptotic activities, as seen in some tumor cell cultures. Complexes featuring oleic acid (OA) with human alpha-lactalbumin (hAl) or with bovine alpha-lactalbumin (bAl), and human lactoferrin (hLf) were investigated using small-angle neutron scattering (SANS). It was shown that while alpha-lactalbumin protein complexes were formed on the surface of polydisperse OA micelles, the lactoferrin complexes comprised a monodisperse system of nanoscale particles. Both hAl and hLf complexes appeared to interact with the chromatin of isolated nuclei affecting chromatin structural organization. The possible roles of these processes in the specific anti-tumor activity of these complexes are discussed.

Colloidally Stable Monolayer Nanosheets with Colorimetric Responses.

Despite the discovery of chromogenic-layered materials for decades of years, fabrication of colloidally stable monolayer organic 2D nanosheets in aqueous media with colorimetric responses is still challenging. Herein reported is the first solution synthesis of chromic monolayer nanosheets via the topochemical polymerization of self-assembled amphiphilic diacetylenes in aqueous media. The polydiacetylene (PDA) nanosheets are ≈3-4 nm thick in solution and only ≈1.9 nm thick in the dried state, while the lateral size can reach several micrometers. Moreover, the aqueous stability endows PDA nanosheets with excellent processability, which can further assemble into films via vacuum filtration or act as an ink for high-resolution inkjet printing. The filtrated films and printed patterns exhibit fully reversible blue-to-red thermochromism, and the film also displays an interesting reversible colorimetric transition in response to near-infrared light, which is not reported for other PDA-only systems. The present colloidal PDA nanosheets should represent a new kind of chromic organic 2D nanomaterials that may be applied as novel building blocks for developing intelligent hybrid materials and may also find diverse sensing, display and/or anticounterfeiting applications.

Nucleation of Hematite: A Nonclassical Mechanism.

Hematite (α-Fe2 O3 ) is thermodynamically stable under ambient conditions, of vast geological importance, and widely used in applications, for example, as corrosion protection and as a pigment. It forms at elevated temperatures, whereas room-temperature reactions typically yield metastable akaganéite or ferrihydrite. The mechanistic key changes underlying this observation were explored in the present study. The entropic contribution to the prenucleation hydrolysis reaction categorically implies the presence of prenucleation clusters (PNCs) as fundamental precursors. The formation of hematite is then due to a change in the reaction mechanism above approximately 50 °C, whereby the reaction limitation towards oxolation in phase-separated clusters is overcome. A model that rationalizes the occurrence of hematite, akaganéite, and ferrihydrite based on the chemistry of olation PNCs is proposed. Supersaturation and the temperature dependence of olation and oxolation rates from monomeric precursors are irrelevant in this nonclassical mechanism.

Inner structure and dynamics of microgels with low and medium crosslinker content prepared via surfactant-free precipitation polymerization and continuous monomer feeding approach.

The preparation of poly(N-isopropylacrylamide) microgels via classical precipitation polymerization (batch method) and a continuous monomer feeding approach (feeding method) leads to different internal crosslinker distributions, i.e., from core-shell-like to a more homogeneous one. The internal structure and dynamics of these microgels with low and medium crosslinker concentrations are studied with dynamic light scattering and small-angle neutron scattering in a wide q-range below and above the volume phase transition temperature. The influence of the preparation method, and crosslinker and initiator concentration on the internal structure of the microgels is investigated. In contrast to the classical conception where polymer microgels possess a core-shell structure with the averaged internal polymer density distribution within the core part, a detailed view of the internal inhomogeneities of the PNIPAM microgels and the presence of internal domains even above the volume phase transition temperature, when polymer microgels are in the deswollen state, are presented. The correlation between initiator concentration and the size of internal domains that appear inside the microgel with temperature increase is demonstrated. Moreover, the influence of internal inhomogeneities on the dynamics of the batch- and feeding-microgels studied with neutron spin-echo spectroscopy is reported.

Synthesis and Characterization of Gelatin-Based Magnetic Hydrogels.

A simple preparation of thermoreversible gelatin-based ferrogels in water provides a constant structure defined by the crosslinking degree for gelatin contents between 6 and 18 wt%. The possibility of varying magnetite nanoparticle concentration between 20 and 70 wt% is also reported. Simulation studies hint at the suitability of collagen to bind iron and hydroxide ions, suggesting that collagen acts as a nucleation seed to iron hydroxide aggregation, and thus the intergrowth of collagen and magnetite nanoparticles already at the precursor stage. The detailed structure of the individual ferrogel components is characterized by small-angle neutron scattering (SANS) using contrast matching. The magnetite structure characterization is supplemented by small-angle X-ray scattering and microscopy only visualizing magnetite. SANS shows an unchanged gelatin structure of average mesh size larger than the nanoparticles with respect to gel concentration while the magnetite nanoparticles size of around 10 nm seems to be limited by the gel mesh size. Swelling measurements underline that magnetite acts as additional crosslinker and therefore varying the magnetic and mechanical properties of the ferrogels. Overall, the simple and variable synthesis protocol, the cheap and easy accessibility of the components as well as the biocompatibility of the gelatin-based materials suggest them for a number of applications including actuators.

Amphibious Polymer Materials with High Strength and Superb Toughness in Various Aquatic and Atmospheric Environments.

Herein, the fabrication of amphibious polymer materials with outstanding mechanical performances, both underwater and in the air is reported. A polyvinyl alcohol/poly(2-methoxyethylacrylate) (PVA/PMEA) composite with multiscale nanostructures is prepared by combining solvent exchange and thermal annealing strategies, which contributes to nanophase separation with rigid PVA-rich and soft PMEA-rich phases and high-density crystalline domains of PVA chains, respectively. Benefiting from the multiscale nanostructure, the PVA/PMEA hydrogel demonstrates excellent stability in harsh (such as acidic, alkaline, and saline) aqueous solutions, as well as superior mechanical behavior with a breaking strength of up to 34.8 MPa and toughness of up to 214.2 MJ m-3 . Dehydrating the PVA/PMEA hydrogel results in an extremely robust plastic with a breaking strength of 65.4 MPa and toughness of 430.9 MJ m-3 . This study provides a promising phase-structure engineering route for constructing high-performance polymer materials for complex load-bearing environments.

Peeling-Stiffening Self-Adhesive Ionogel with Superhigh Interfacial Toughness.

Self-adhesive materials that can directly adhere to diverse solid surfaces are indispensable in modern life and technologies. However, it remains a challenge to develop self-adhesive materials with strong adhesion while maintaining its intrinsic softness for efficient tackiness. Here, a peeling-stiffening self-adhesive ionogel that reconciles the seemingly contradictory properties of softness and strong adhesion is reported. The ionogel contains two ionophilic repeating units with distinct associating affinities, which allows to adaptively wet rough surface in the soft dissipating state for adhering, and to dramatically stiffen to the glassy state upon peeling. The corresponding modulus increases by 117 times driven by strain-rate-induced phase separation, which greatly suppresses crack propagation and results in a super high interfacial toughness of 8046 J m-2 . The self-adhesive ionogel is also transparent, self-healable, recyclable, and can be easily removed by simple moisture treatment. This strategy provides a new way to design high-performance self-adhesive materials for intelligent soft devices.

Self-compliant ionic skin by leveraging hierarchical hydrogen bond association.

Robust interfacial compliance is essential for long-term physiological monitoring via skin-mountable ionic materials. Unfortunately, existing epidermal ionic skins are not compliant and durable enough to accommodate the time-varying deformations of convoluted skin surface, due to an imbalance in viscosity and elasticity. Here we introduce a self-compliant ionic skin that consistently works at the critical gel point state with almost equal viscosity and elasticity over a super-wide frequency range. The material is designed by leveraging hierarchical hydrogen bond association, allowing for the continuous release of polymer strands to create topological entanglements as complementary crosslinks. By embodying properties of rapid stress relaxation, softness, ionic conductivity, self-healability, flaw-insensitivity, self-adhesion, and water-resistance, this ionic skin fosters excellent interfacial compliance with cyclically deforming substrates, and facilitates the acquisition of high-fidelity electrophysiological signals with alleviated motion artifacts. The presented strategy is generalizable and could expand the applicability of epidermal ionic skins to more complex service conditions.

A Solid-Liquid Bicontinuous Fiber with Strain-Insensitive Ionic Conduction.

Stretchable ionic conductors are crucial for enabling advanced iontronic devices to operate under diverse deformation conditions. However, when employed as interconnects, existing ionic conductors struggle to maintain stable ionic conduction under strain, hindering high-fidelity signal transmission. Here, it is shown that strain-insensitive ionic conduction can be achieved by creating a solid-liquid bicontinuous microstructure. A bicontinuous fiber from polymerization-induced phase separation, which contains a solid elastomer phase interpenetrated by a liquid ion-conducting phase, is fabricated. The spontaneous partitioning of dissolved salts leads to the formation of a robust self-wrinkled interface, fostering the development of highly tortuous ionic channels. Upon stretch, these meandering ionic channels are straightened, effectively enhancing ionic conductivity to counteract the strain effect. Remarkably, the fiber retains highly stable ionic conduction till fracture, with only 7% resistance increase at 200% strain. This approach presents a promising avenue for designing durable ionic cables capable of signal transmission with minimal strain-induced distortion.

Piezoionic Elastomers by Phase and Interface Engineering for High-Performance Energy-Harvesting Ionotronics.

Piezoionic materials play a pivotal role in energy-harvesting ionotronics. However, a persistent challenge lies in balancing the structural requirements for voltage generation, current conduction, and mechanical adaptability. The conventional approach of employing crystalline heterostructures for stress concentration and localized charge separation, while effective for voltage generation, often compromises the stretchability and long-range charge transport found in homogeneous quasisolid states. Herein, phase and interface engineering strategy is introduced to address this dilemma and a piezoionic elastomer is presented that seamlessly integrates ionic liquids and ionic plastic crystals, forming a finely tuned microphase-separated structure with an intermediate phase. This approach promotes charge separation via stress concentration among hard phases while leveraging the high ionic charge mobility in soft and intermediate phases. Impressively, the elastomer achieves an extraordinary piezoionic coefficient of about 6.0 mV kPa-1, a more than threefold improvement over current hydrogels and ionogels. The resulting power density of 1.3 µW cm-3 sets a new benchmark, exceeding that of state-of-the-art piezoionic gels. Notably, this elastomer combines outstanding stretchability, remarkable toughness, and rapid self-healing capability, underscoring its potential for real-world applications. This work may represent a stride toward mechanically robust energy harvesting systems and provide insights into ionotronic systems for human-machine interaction.

Amorphous 1-D nanowires of calcium phosphate/pyrophosphate: A demonstration of oriented self-growth of amorphous minerals.

Amorphous inorganic solids are traditionally isotropic, thus, it is believed that they only grow in a non-preferential way without the assistance of regulators, leading to the morphologies of nanospheres or irregular aggregates of nanoparticles. However, in the presence of (ortho)phosphate (Pi) and pyrophosphate ions (PPi) which have synergistic roles in biomineralization, the highly elongated amorphous nanowires (denoted ACPPNs) form in a regulator-free aqueous solution (without templates, additives, organics, etc). Based on thorough characterization and tracking of the formation process (e.g., Cryo-TEM, spherical aberration correction high resolution TEM, solid state NMR, high energy resolution monochromated STEM-EELS), the microstructure and its preferential growth behavior are elucidated. In ACPPNs, amorphous calcium orthophosphate and amorphous calcium pyrophosphate are distributed at separated but close sites. The ACPPNs grow via either the preferential attachment of ∼2 nm nanoclusters in a 1-dimension way, or the transformation of bigger nanoparticles, indicating an inherent driving force-governed process. We propose that the anisotropy of ACPPNs microstructure, which is corroborated experimentally, causes their oriented growth. This study proves that, unlike the conventional view, amorphous minerals can form via oriented growth without external regulation, demonstrating a novel insight into the structures and growth behaviors of amorphous minerals.

Aqueous spinning of robust, self-healable, and crack-resistant hydrogel microfibers enabled by hydrogen bond nanoconfinement.

Robust damage-tolerant hydrogel fibers with high strength, crack resistance, and self-healing properties are indispensable for their long-term uses in soft machines and robots as load-bearing and actuating elements. However, current hydrogel fibers with inherent homogeneous structure are generally vulnerable to defects and cracks and thus local mechanical failure readily occurs across fiber normal. Here, inspired by spider spinning, we introduce a facile, energy-efficient aqueous pultrusion spinning process to continuously produce stiff yet extensible hydrogel microfibers at ambient conditions. The resulting microfibers are not only crack-insensitive but also rapidly heal the cracks in 30 s by moisture, owing to their structural nanoconfinement with hydrogen bond clusters embedded in an ionically complexed hygroscopic matrix. Moreover, the nanoconfined structure is highly energy-dissipating, moisture-sensitive but stable in water, leading to excellent damping and supercontraction properties. This work creates opportunities for the sustainable spinning of robust hydrogel-based fibrous materials towards diverse intelligent applications.

Highly Damping and Self-Healable Ionic Elastomer from Dynamic Phase Separation of Sticky Fluorinated Polymers.

Shock-induced low-frequency vibration damage is extremely harmful to bionic soft robots and machines that may incur the malfunction of fragile electronic elements. However, current skin-like self-healable ionic elastomers as the artificial sensing and protecting layer still lack the ability to dampen vibrations, due to their almost opposite design for molecular frictions to material's elasticity. Inspired by the two-phase structure of adipose tissue (the natural damping skin layer), here, a highly damping ionic elastomer with energy-dissipating nanophases embedded in an elastic matrix is introduced, which is formed by polymerization-induced dynamic phase separation of sticky fluorinated copolymers in the presence of lithium salts. Such a supramolecular design decouples the elastic and damping functions into two distinct phases, and thus reconciles a few intriguing properties including ionic conductivity, high stretchability, softness, strain-stiffening, elastic recovery, room-temperature self-healability, recyclability, and most importantly, record-high damping capacity at the human motion frequency range (loss factor tan δ > 1 at 0.1-50 Hz). This study opens the door for the artificial syntheses of high-performance damping ionic skins with robust sensing and protective applications in soft electronics and robotics.

Multiscale Structural Insight into Dairy Products and Plant-Based Alternatives by Scattering and Imaging Techniques.

Dairy products and plant-based alternatives have a large range of structural features from atomic to macroscopic length scales. Scattering techniques with neutrons and X-rays provide a unique view into this fascinating world of interfaces and networks provided by, e.g., proteins and lipids. Combining these scattering techniques with a microscopic view into the emulsion and gel systems with environmental scanning electron microscopy (ESEM) assists in a thorough understanding of such systems. Different dairy products, such as milk, or plant-based alternatives, such as milk-imitating drinks, and their derived or even fermented products, including cheese and yogurt, are characterized in terms of their structure on nanometer- to micrometer-length scales. For dairy products, the identified structural features are milk fat globules, casein micelles, CCP nanoclusters, and milk fat crystals. With increasing dry matter content in dairy products, milk fat crystals are identified, whereas casein micelles are non-detectable due to the protein gel network in all types of cheese. For the more inhomogeneous plant-based alternatives, fat crystals, starch structures, and potentially protein structures are identified. These results may function as a base for improving the understanding of dairy products and plant-based alternatives, and may lead to enhanced plant-based alternatives in terms of structure and, thus, sensory aspects such as mouthfeel and texture.

Fluoroalkyl-grafted mesoporous silica antireflective films with enhanced stability in vacuum.

A new antireflective silica film with closed mesopores was successfully prepared for the optical elements used in vacuum of a high-power laser system. The ordered cagelike mesopores were formed with the direction of surfactant F127 and then closed by long-chain fluoroalkylsilane. The grazing incident x-ray diffraction and grazing incident small-angle x-ray scattering results indicated that the mesopores in film constructed a body-center cubic structure. The films exhibited excellent transmittance as high as 99.98% on quartz substrate. After a 1-month antipollution test with polydimethylsiloxane in vacuum, the decrease of transmittance was small as 0.02%. This film had a high laser-induced damage threshold of above 28 J/cm(2) at 1 ns laser pulse of 1053 nm wavelength.